JP6615554B2 - Olefin-based resin, production method and composition thereof, and molded article - Google Patents

Description

  The present invention relates to an olefin resin including a graft polymer having a main chain composed of an ethylene polymer and a side chain composed of a propylene polymer, a method for producing the resin, and a propylene resin including the resin The present invention relates to a composition, a molded product obtained from the resin, and a molded product obtained from the resin composition.

  Polyolefin resins such as polyethylene and polypropylene are low in production energy, light weight, and excellent in recyclability, so to 3R (Reduce, Reuse, Recycle) to form a recycling society in each industry. Attention has increased further in the efforts. Polyolefin resins are used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automobile parts, etc. One type of polymer may be used alone. However, it is used as a resin composition containing a plurality of resins depending on the required performance.

  For example, linear low-density polyethylene resin is used for packaging materials because of its excellent impact resistance, cold resistance, and transparency, but its heat resistance and rigidity are inferior, so a propylene resin composition blended with a propylene resin Often used as a product. In particular, packaging containers for food and medical use are required to have a high balance of various physical properties and transparency (visibility of contents) in addition to various physical properties such as low-temperature impact resistance, heat resistance, and rigidity.

A propylene-based resin composition having improved impact resistance using a low-density polyethylene resin or a linear low-density polyethylene resin and further using a propylene-ethylene block copolymer and a nucleating agent is known (for example, Patent Document 1).
A propylene-based resin composition in which impact resistance is improved by blending an ethylene-based resin into a propylene block copolymer and having specific physical properties is known (for example, see Patent Documents 2 and 3).

  Patent Document 4 discloses a propylene-based resin composition containing a specific polypropylene resin, a specific ethylene / α-olefin copolymer, and a nucleating agent, and a molded product and a container obtained from the composition. Are known.

  As described above, in order to produce a packaging container having a good balance of mechanical properties such as rigidity, heat resistance and impact resistance, it has been performed to add an ethylene resin to a propylene resin. It is known that the composition thus obtained is inferior in transparency as compared with the case of a simple propylene resin, and an ethylene resin that has both excellent mechanical property balance and high transparency and its transparency A propylene resin composition has been desired.

JP 2001-26686 A JP 2002-187996 A Japanese Patent Laid-Open No. 2002-187997 International Publication No. 2010/074001

  To provide an olefin-based resin and a propylene-based resin composition excellent in balance between various properties such as heat resistance and impact resistance and transparency.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin containing a graft polymer having a main chain composed of an ethylene polymer and a side chain composed of a propylene polymer has a heat resistance. It was found that the balance between the property and transparency and the balance between the impact resistance and the transparency are excellent.

That is, the present invention relates to the following [1] to [14], for example.
[1] A graft polymer [R1] having a main chain composed of an ethylene-based polymer and a side chain composed of a propylene-based polymer and satisfying the following requirement (i): Satisfies olefin resin (β).

(I) The ethylene polymer constituting the main chain has a repeating unit derived from ethylene, and is a repeating unit derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. In the range of 0 mol% or more and less than 10 mol% in the main chain.
(I) The density is in the range of 895 to 925 kg / m ³ .

[2] The olefin resin (β) according to [1], which satisfies the following requirement (II).
(II) The melting point (Tm ₁ ) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165 ° C.

[3] The olefin resin (β) according to [1] or [2], which satisfies the following requirement (III).
(III) The insoluble amount of hot xylene is less than 3.0% by mass.

[4] The olefin resin (β) according to any one of [1] to [3], wherein the graft polymer [R1] satisfies the following requirement (ii).
(Ii) The propylene-based polymer constituting the side chain has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain, and at least selected from ethylene and an α-olefin having 4 to 20 carbon atoms. It has a repeating unit derived from one α-olefin in the range of 0 to 5 mol% in the side chain.

[5] The olefin resin (β) according to any one of [1] to [4], wherein the graft polymer [R1] satisfies the following requirement (iii).
(Iii) The isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain is 93% or more.

[6] The olefin resin (β) according to any one of [1] to [5], which satisfies the following requirement (IV).
(IV) The ratio of the repeating unit derived from ethylene is in the range of 10 to 95 mol% with respect to all repeating units.

[7] The method for producing an olefin resin (β) according to any one of [1] to [6], including the following steps (A) and (B):
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Step (B) Unsaturated terminal polypropylene produced in the following step (B1) or (B2) (B1) (A), which is carried out in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table A step of copolymerizing ethylene with at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms (B2) unsaturated terminal polypropylene produced in (A), and ethylene Copolymerization process

  [8] The method for producing an olefin resin (β) according to [7], wherein the group 4 transition metal compound of the periodic table is a bridged metallocene compound represented by the following general formula [B].

（式［Ｂ］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち相互に隣り合う二つの基同士は互いに結合して環を形成していてもよい。

(In the formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. A hetero atom-containing group is shown, and two groups adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R ⁶ and R ⁷ may bond to each other to form a ring, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represents an aryl group.
Y ¹ represents a carbon atom or a silicon atom.
M ¹ represents a zirconium atom or a hafnium atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

  [9] The method for producing an olefin resin (β) according to [7] or [8], wherein the step (B) is a solution polymerization process having a polymerization temperature of 90 ° C. or higher.

  [10] A propylene resin composition containing the propylene resin (α) and the olefin resin (β) according to any one of [1] to [6].

  [11] 50 to 98 parts by mass of the propylene resin (α) and 2 to 50 parts by mass of the olefin resin (β) (the total of the propylene resin (α) and the olefin resin (β) is 100 parts by mass. ) Containing the propylene-based resin composition according to [10].

  [12] In the above [10] or [11], the olefin resin (β) is obtained by the method for producing an olefin resin (β) according to any one of [7] to [9]. The propylene-based resin composition described.

  [13] A molded product obtained from the olefin resin (β) according to any one of [1] to [6].

  [14] A molded product obtained from the propylene-based resin composition according to any one of [10] to [12].

  The olefin resin of the present invention is excellent in balance between physical properties such as heat resistance and impact resistance and transparency, and the present invention can further provide a propylene resin composition containing the olefin resin. .

In Examples 1-4 and Comparative Examples 1-3, it is the figure which plotted the relationship between TMA softening temperature and haze.

Hereinafter, the olefin resin (β), the method for producing the olefin resin (β), the propylene resin composition, and the molded body of the present invention will be described in detail.
<Olefin resin (β)>
The olefin resin (β) of the present invention comprises a graft polymer [R1] having a main chain composed of an ethylene polymer and a side chain composed of a propylene polymer and satisfying the following requirement (i). Including the following requirements (I).

  The olefin resin (β) preferably satisfies the following requirement (II), preferably satisfies the following requirement (III), and preferably satisfies the following requirement (IV). That is, the olefin resin (β) preferably satisfies one or more of the following requirements (II) to (IV), more preferably satisfies two or more, and most preferably satisfies three. The olefin resin (β) preferably satisfies the following requirement (V).

  The olefin resin (β) may be composed of only the graft polymer [R1], or may be composed of the graft polymer [R1] and one or more other olefin polymers. May be. The graft polymer [R1] constituting the olefin resin (β) may be one kind of polymer or two or more kinds of polymers.

  Examples of the other olefin polymer include terminal unsaturated polypropylene when the olefin resin (β) is produced by the production method described later. In the production method described later, the terminal unsaturated polypropylene produced in the step (A) is used in the step (B), and all or a part of the terminal unsaturated polypropylene is bonded to the side chain of the graft polymer [R1]. However, a part does not contribute to the copolymerization in the step (B) and can be contained in the olefin resin (β). The olefin resin (β) of the present invention contains the graft polymer [R1] in an amount of usually 95 to 5% by mass, preferably 80 to 10% by mass, in 100% by mass of the resin.

(I) The density is in the range of 895 to 925 kg / m ³ . The density is a value measured according to JIS K7112.
(II) The melting point (Tm ₁ ) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165 ° C.
(III) The insoluble amount of hot xylene is less than 3.0% by mass.
(IV) The ratio of the repeating unit derived from ethylene is in the range of 10 to 95 mol% with respect to all repeating units.
(V) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 5.0 dl / g.
Hereinafter, the graft polymer [R1] and the above requirements (I) to (V) will be specifically described.

[Graft polymer [R1]]
The olefin resin (β) contains the graft polymer [R1] as an essential constituent. The graft polymer [R1] is a graft polymer having a main chain composed of an ethylene polymer and a side chain composed of a propylene polymer.
In the present invention, the term “graft polymer” is a polymer in which one or more side chains are bonded to the main chain.

  The graft polymer [R1] includes a graft polymer [R1] because it has a structure in which a side chain composed of a propylene polymer is chemically bonded to a main chain composed of an ethylene polymer. The olefin-based resin (β) is effectively imparted with heat resistance and rigidity derived from the propylene-based polymer as compared with a simple ethylene-based polymer or a blend of an ethylene-based polymer and a propylene-based polymer. Furthermore, since the olefin resin (β) contains the graft polymer [R1], the ethylene polymer and the propylene polymer can be favorably dispersed, and thus the transparency is excellent. Further, when a composition containing an olefin resin (β) and a propylene resin is used, the graft polymer [R1] exhibits high compatibility with the propylene resin, and thus the olefin resin (β) is satisfactorily used. Dispersed in a propylene-based resin, exhibits impact resistance and toughness derived from an ethylene-based polymer, and is excellent in transparency.

  As described above, the graft polymer [R1] is a graft copolymer having a main chain and a side chain. The graft polymer [R1] satisfies the following requirement (i). The graft polymer [R1] preferably satisfies the following requirement (ii), and preferably satisfies the following requirement (iii). That is, the graft polymer [R1] preferably satisfies one or more of the following requirements (ii) and (iii), and more preferably satisfies two.

  (I) The ethylene polymer constituting the main chain has a repeating unit derived from ethylene, and the repeating unit is derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. In the main chain in the range of 0 mol% or more and less than 10 mol%.

  (Ii) The propylene-based polymer constituting the side chain has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain, and is at least selected from ethylene and an α-olefin having 4 to 20 carbon atoms. It has a repeating unit derived from one α-olefin in the range of 0 to 5 mol% in the side chain.

(Iii) The isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain is 93% or more.
The graft polymer [R1] more preferably satisfies the following requirement (iv), and more preferably satisfies the following requirement (v). That is, the graft polymer [R1] more preferably satisfies at least one of the following requirements (iv) and (v), and particularly preferably satisfies two.

(Iv) The weight average molecular weight of the ethylene polymer constituting the main chain is 50,000 to 500,000.
(V) The propylene polymer constituting the side chain has a weight average molecular weight of 5,000 to 100,000.

Hereinafter, these requirements (i) to (v) will be specifically described.
[Requirement (i)]
The main chain of the graft polymer [R1] is composed of an ethylene polymer. The ethylene polymer constituting the main chain has a repeating unit derived from ethylene, and the repeating unit derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. It has in the range of 0 mol% or more and less than 10 mol%.

  That is, the ethylene-based polymer has a repeating unit derived from ethylene as an essential structural unit, and a repeating unit derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms, You may have as an arbitrary structural unit.

  From the viewpoint of expressing properties such as flexibility and low temperature properties, the ethylene polymer is composed of a repeating unit derived from ethylene and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. A polymer composed of a repeating unit to be led is preferable.

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1- Hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl- 1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl -1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene , 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like can be given.

  The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 10 carbon atoms, and more preferably an α-olefin having 3 to 8 carbon atoms. Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene, 3-methyl-1-pentene, Examples thereof include branched olefins such as 3-methyl-1-butene, among which propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene, 1-pentene and 1-hexene are preferable. 1-octene is more preferable. By using 1-butene, 1-pentene, 1-hexene, or 1-octene as an α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene, it balances the most flexible and low temperature characteristics with good mechanical properties. can do.

  The ratio of the repeating unit derived from ethylene in the ethylene polymer constituting the main chain of the graft polymer [R1] is usually 90 mol% or more and less than 100 mol% in the main chain, preferably 92 to 99.99. The range is 9 mol%, more preferably 94 to 99 mol%, and still more preferably 95 to 98 mol%. “In the main chain” means a ratio when the total repeating unit contained in the main chain is 100 mol%.

  In the ethylene polymer constituting the main chain of the graft polymer [R1], the proportion of repeating units derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms is as follows: It is 0 mol% or more and less than 10 mol% in the main chain, preferably 0.1 to 8 mol%, more preferably 1 to 6 mol%, still more preferably 2 to 5 mol%.

  As the ratio of the repeating unit derived from ethylene and the repeating unit derived from α-olefin in the main chain is in the above range, while maintaining the characteristics of the ethylene polymer such as flexibility and low temperature characteristics, as a side chain Since the difference in refractive index from the propylene-based polymer contained is small, the transparency is also excellent. In addition, even when blended with a propylene resin, high transparency can be achieved while maintaining the characteristics of the propylene resin such as rigidity and heat resistance and the properties of the ethylene polymer such as flexibility and low temperature characteristics. . On the other hand, if the repeating unit derived from α-olefin exceeds 10 mol percent, the difference in refractive index from the propylene-based polymer becomes large, resulting in poor transparency.

  The molar ratio of the repeating unit derived from ethylene and the repeating unit derived from α-olefin in the main chain is the ratio between the concentration of ethylene and the concentration of α-olefin present in the polymerization reaction system in the step of producing the main chain. It can be adjusted by controlling.

  In addition, the molar ratio (mol%) of the repeating unit derived from ethylene contained in the main chain and the repeating unit derived from α-olefin is, for example, ethylene · α obtained under a condition not containing terminal unsaturated polypropylene described later. -It calculates | requires from calculating | requiring the alpha-olefin composition of an olefin copolymer by a conventional method, and deducting the influence derived from a terminal unsaturated polypropylene and a side chain from the alpha-olefin composition of an olefin resin ((beta)).

[Requirement (ii)]
The side chain of the graft polymer [R1] is composed of a propylene polymer. The propylene-based polymer constituting the side chain has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain, and at least one selected from ethylene and α-olefins having 4 to 20 carbon atoms. It has a repeating unit derived from an α-olefin in the range of 0 to 5 mol% in the side chain.

  The propylene polymer constituting the side chain is preferably selected from ethylene and an α-olefin having 4 to 20 carbon atoms having a repeating unit derived from propylene in the range of 99.5 to 100 mol% in the side chain. The repeating unit derived from at least one α-olefin is in the range of 0 to 0.5 mol% in the side chain.

“In the side chain” means a ratio when the total repeating unit contained in the side chain is 100 mol%.
That is, the propylene-based polymer constituting the side chain contains a small amount of at least one α-olefin selected from ethylene other than propylene and an α-olefin having 4 to 20 carbon atoms within a range not impairing its role and characteristics. It may be polymerized.

[Requirements (iii)]
In the graft polymer [R1], the isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain is 93% or more.

  Since the side chain of the graft polymer [R1] has the above characteristics, the side chain exhibits crystallinity and has a melting point. When the side chain of the graft polymer [R1] is an isotactic polypropylene polymer having a high melting point, the heat resistance of the olefin resin (β) is enhanced. Furthermore, the fact that the side chain of the graft polymer [R1] is an isotactic polypropylene polymer increases the compatibility of the olefin resin (β) with the propylene resin. For this reason, the propylene-based resin composition obtained by satisfying the requirement (iii) is preferable because it can maintain good rigidity and hardness while exhibiting good impact resistance.

  The graft polymer [R1] is a copolymer of terminally unsaturated polypropylene produced in step (A), ethylene, and optionally used α-olefin in the production step (B) of the olefin resin (β) described later. Can be obtained. That is, the composition and stereoregularity of the terminal unsaturated polypropylene correspond to the side chain composition and stereoregularity of the graft polymer [R1]. Therefore, the composition and stereoregularity of the terminal unsaturated polypropylene produced in the step (A) are calculated using a known method, and the composition and stereoregularity are calculated based on the composition of the side chain and the stereoregularity of the graft polymer [R1]. Can be defined as sex.

[Requirement (iv)]
In the graft polymer [R1], the ethylene polymer constituting the main chain has a weight average molecular weight of 50,000 to 500,000.

The weight average molecular weight is preferably in the range of 80,000 to 300,000, more preferably in the range of 100,000 to 200,000.
The said weight average molecular weight is a weight average molecular weight of polyethylene conversion calculated | required by gel permeation chromatography (GPC).

  When the weight average molecular weight of the ethylene polymer constituting the main chain of the graft polymer [R1] is in the above range, the moldability (fluidity) of the resin while maintaining the mechanical strength in the olefin resin (β). Can be improved. Furthermore, the propylene resin composition containing the olefin resin (β) also tends to have a better balance between rigidity and toughness.

  On the other hand, if the weight average molecular weight is less than 50,000, the mechanical strength of the olefin resin (β) may be lowered, and it may be difficult to obtain a good balance of physical properties. In the propylene-based resin composition to be included, the mechanical strength is similarly lowered, and it may be difficult to obtain a good balance of physical properties. If the weight average molecular weight is greater than 500,000, the moldability of the olefin resin (β) may be deteriorated and may not be compatible with various molding processes. Even in the resulting propylene resin, dispersion into the propylene resin is possible. Defects may occur and it may be difficult to obtain a desired physical property balance.

  The weight average molecular weight of the ethylene polymer constituting the main chain of the graft polymer [R1] can be adjusted by controlling the ethylene concentration in the polymerization system in the production process described later. Examples of the ethylene concentration control method include adjustment of ethylene partial pressure and polymerization temperature. The weight average molecular weight of the ethylene polymer constituting the main chain can be adjusted by supplying hydrogen into the polymerization system.

  The weight average molecular weight of the ethylene polymer constituting the main chain can be determined, for example, by analyzing the ethylene polymer produced under the condition that does not contain terminal unsaturated polypropylene, which will be described later, or the olefin resin (β). It is calculated | required from analyzing and deducting the influence derived from a terminal unsaturated polypropylene and a side chain.

[Requirement (v)]
In the graft polymer [R1], the weight average molecular weight of the propylene polymer constituting the side chain is 5,000 to 100,000.

  That is, the graft polymer [R1] has a structure in which a macromonomer, which is a propylene polymer having a weight average molecular weight of 5,000 to 100,000, is bonded to an ethylene polymer constituting the main chain. And a propylene polymer site | part becomes a side chain. The weight average molecular weight is preferably in the range of 5,000 to 60,000, more preferably 10,000 to 60,000.

  Since the weight average molecular weight of the propylene polymer constituting the side chain of the graft polymer [R1] is in the above range, the olefin resin (β) is excellent in heat resistance and rigidity, and is also excellent in transparency. Furthermore, even in a propylene resin composition containing an olefin resin (β), both good physical property balance and transparency can be achieved.

  If the weight average molecular weight of the propylene polymer constituting the side chain of the graft polymer [R1] is less than 5,000, the compatibilizing effect between the propylene polymer and the ethylene polymer is not sufficient, and the above-mentioned It may be difficult to achieve both the balance of physical properties and transparency.

  When the weight average molecular weight of the propylene polymer constituting the side chain of the graft polymer [R1] is greater than 100,000, the fluidity of the olefin resin (β) is deteriorated, and the processability is deteriorated. There is a case. In addition, even in a propylene resin composition containing an olefin resin (β), poor dispersion due to poor fluidity of the olefin resin (β) occurs and not only the transparency is deteriorated but also the mechanical properties are deteriorated. There is.

In addition, the weight average molecular weight of the propylene-type polymer which comprises a side chain can be calculated | required from the terminal unsaturated polypropylene produced | generated at a process (A) similarly to description of the "requirement (iii)" mentioned above. That is, it can be determined by measuring the weight average molecular weight of the terminal unsaturated polypropylene produced in the step (A) by a conventional method. For example, the weight average molecular weight in terms of polypropylene of the terminal unsaturated polypropylene obtained by gel permeation chromatography (GPC) can be used as the weight average molecular weight of the propylene-based polymer constituting the side chain.
Examples of the method for adjusting the weight average molecular weight of the propylene polymer constituting the side chain include a method of adjusting the polymerization temperature and the polymerization pressure in the production step (A) described later.

[Requirement (I)]
The olefin resin (β) has a density in the range of 895 to 925 kg / m ³ . Preferably it exists in the range of 900-920 kg / m < ³ >. By being in this range, the density difference between the ethylene polymer and the propylene polymer is small and the transparency is excellent. It can adjust to the said range by adjusting the ratio of an ethylene polymer and a propylene polymer at the time of manufacture, or adjusting the repeating unit guide | induced from the alpha-olefin of an ethylene polymer. As described above, the density is a value measured according to JIS K7112.

[Requirement (II)]
The olefin resin (β) has a melting point (Tm ₁ ) measured by differential scanning calorimetry (DSC) in the range of 120 to 165 ° C, preferably in the range of 130 to 160 ° C, and 135 to 160 ° C. It is more preferable that it is in the range.

  That is, the olefin resin (β) has a melting peak measured by differential scanning calorimetry (DSC) in the range of 120 to 165 ° C, preferably 130 to 160 ° C, more preferably 135 to 160 ° C.

The temperature at which the melting peak appears, that is, the melting point (Tm ₁ ) and the heat of fusion (ΔH) to be described later, The endothermic peak that appears in the temperature raising step (temperature raising rate 10 ° C./min) is analyzed.

The melting point (Tm ₁ ) and heat of fusion (ΔH) observed in the above range are mainly attributed to the polypropylene side chain of the graft polymer [R1] constituting the olefin resin (β). When the melting point (Tm ₁ ) is in the above range, and more preferably, the heat of fusion (ΔH) is in the range described later, the olefin resin (β) can be well compatible with the propylene resin, The propylene resin composition containing the olefin resin (β) and the propylene polymer has a good balance of rigidity, heat resistance and toughness. Examples of a method for adjusting the melting point (Tm ₁ ) within the above range include a method for adjusting the polymerization temperature and the polymerization pressure in the production step (A) described later.

[Requirement (III)]
The olefin resin (β) has an insoluble amount of thermal xylene of less than 3.0% by mass, preferably less than 2.5% by mass, more preferably less than 2.0% by mass.

The thermal xylene insoluble amount is a value calculated by the following method.
The sample is formed into a sheet having a thickness of 0.4 mm by hot pressing (180 ° C., heating for 5 minutes, cooling for 1 minute) and cut into pieces. About 100 mg is weighed, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene at 140 ° C. for 3 hours in a sealed container. Next, the screen is taken out and dried at 80 ° C. for 2 hours or more until a constant weight is obtained. The thermal xylene insoluble amount (wt%) is represented by the following formula.

Thermal xylene insoluble amount (wt%) = 100 × (W3-W2) / (W1-W2)
W1: Total mass of screen and sample before test, W2: Mass of screen, W3: Total mass of screen and sample after test When olefin resin (β) satisfies requirement (III), olefin resin Since (β) contains no or even a small amount of a hot xylene-insoluble component, it can be well dispersed in the propylene polymer, and as a result, a desired effect is exhibited. On the other hand, when the insoluble amount of hot xylene is 3 wt% or more, an appearance defect called lumps may occur in a molded product obtained from the propylene-based resin composition.

  As shown in the production method described later, an olefin resin (β) having a thermal xylene-insoluble component in the above range can be obtained by adopting a method of obtaining a graft polymer directly from the polymerization step.

[Requirement (IV)]
In the olefin resin (β), the proportion of repeating units derived from ethylene is in the range of 10 to 95 mol% with respect to all repeating units. It is preferably in the range of 20 to 90 mol%, more preferably in the range of 30 to 90 mol%.

  When the repeating unit derived from ethylene is in the above range, the olefin resin (β) is in a mode that includes an ethylene polymer and a propylene polymer in a well-balanced manner, and has characteristics derived from the respective polymers. Transparency can be expressed well while being utilized.

[Requirement (V)]
The olefin resin (β) has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.5 to 5.0 dl / g. The intrinsic viscosity [η] is preferably 1.0 to 4.0 dl / g, more preferably 1.0 to 3.0 dl / g. When the intrinsic viscosity [η] is in the above range, the olefin resin (β) has sufficient mechanical strength and also has good moldability.
The olefin resin (β) preferably satisfies one or more of the following requirements (VI) to (VII).

[Requirement (VI)]
The olefin resin (β) preferably has a heat of fusion (ΔH) of a melting peak showing a melting point (Tm ₁ ) in the range described in the requirement (II) in the range of ₁ to 90 J / g, It is more preferably in the range of 80 J / g, particularly preferably in the range of 3 to 70 J / g.

  Examples of the method for adjusting the heat of fusion (ΔH) within the above range include a method for adjusting the amount of terminal unsaturated polypropylene produced in the production step (A) in the production step (B) described later.

[Requirements (VII)]
The olefin-based resin (β) has a melting peak (Tm ₂ ) measured by differential scanning calorimetry (DSC) in the range described in the above requirement (II) in the range of 90 to 119 ° C. separately from the melting point (Tm ₁ ). It is preferably in the range, and more preferably in the range of 100 to 116 ° C.

  The temperature at which the melting peak appears is that the sample is once melted by DSC in the heating step and then crystallized by the cooling step up to 30 ° C. and then appears in the second heating step (heating rate 10 ° C./min). This is an analysis of the endothermic peak.

  The melting peak is attributed to the main chain composed of the ethylene polymer of the graft polymer [R1] constituting the olefin resin (β). When it has a melting peak in the above range, the olefin resin (β) is preferable because it is excellent in heat resistance and mechanical properties, and has a small density difference from the propylene polymer and excellent transparency. As a method for obtaining an olefin resin (β) having a melting peak in the above range, a ratio of an ethylene polymer and a propylene polymer is adjusted during production, or a repeating unit derived from an α-olefin of an ethylene polymer is used. The method of adjusting is mentioned.

The olefin resin (β) includes a graft polymer [R1] having a main chain composed of an ethylene polymer and a side chain composed of a propylene polymer as described above, and has a density of 895 to 925 kg / m ³ . It is in. Therefore, the olefin resin (β) does not exhibit physical properties like ordinary elastomers. For example, the elastic recovery rate from 300% elongation of the olefin resin (β) is usually 70% or less, preferably 50% or less, and more preferably 30% or less. When the elastic recovery rate from 300% elongation is in the above range, the difference in density between the ethylene polymer and the propylene polymer is small, which is a cause of good expression of transparency.

The olefin-based resin (β) preferably does not contain substances that cause coloring, off-flavor, and contamination of the final product.
Specific examples of substances that cause coloring, off-flavours, and contamination of the final product include heteroatom-containing compounds, and the heteroatom-containing compounds contain halogen atoms such as chlorine atoms and bromine atoms. Examples thereof include compounds, compounds containing chalcogen atoms such as acid atoms and sulfur atoms, and compounds containing pnictogen atoms such as nitrogen atoms and phosphorus atoms. Specific examples of the compound containing an oxygen atom include maleic anhydride and a maleic anhydride reactant.

  Examples of substances that cause coloring, off-flavor, and contamination of the final product include metal atom-containing compounds. Specifically, alkali metal-containing compounds such as sodium and potassium, alkaline earth such as magnesium and calcium, and the like. A metal-containing compound.

  In the olefin resin (β), the content of the hetero atom-containing compound is preferably 1000 ppm or less, more preferably 100 ppm or less, and even more preferably 10 ppm or less. In the olefin resin (β), the content of the metal atom-containing compound is preferably 1000 ppm or less, more preferably 100 ppm or less, and still more preferably 10 ppm or less.

<Method for producing olefin resin (β)>
The above-mentioned olefin resin (β) is produced by, for example, a production method including the following steps (A) and (B).

(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Step (B) Unsaturated terminal polypropylene produced in step (B1) or (B2) of (B1) or (B2) below, which is carried out in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table A step of copolymerizing ethylene with at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms (B2) unsaturated terminal polypropylene produced in (A), and ethylene Step of copolymerization Hereinafter, steps (A) and (B) will be described in order.

[Process (A)]
Step (A) is a step of producing terminally unsaturated polypropylene that is a raw material for a side chain composed of a propylene-based polymer of graft type polymer [R1].

  In this step, propylene is polymerized in the presence of a catalyst for olefin polymerization containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. It is a process to do.

  In the present invention, the terminal unsaturated polypropylene means a polypropylene having terminal unsaturation represented by the following terminal structures (I) to (IV). “Poly” in the terminal structures (I) to (IV) represents a bonding position between the terminal structure and a propylene polymer molecular chain other than the terminal structure.

  The proportion of terminal unsaturation in the terminal unsaturated polypropylene is usually 0.1 to 6 per 1000 carbon atoms, preferably 0.4 to 3.0. Further, the terminal unsaturation ratio represented by the terminal structure (I) generally called terminal vinyl is usually 0.1 to 2.0 per 1000 carbon atoms, preferably 0.2 to 2 In the range of 0.

The terminal unsaturation is determined by determining the terminal structure of the terminal unsaturated polypropylene by ¹ H-NMR. ¹ H-NMR may be measured according to a conventional method. The end structure can be assigned according to the method described in Macromolecular Rapid Communications 2000, 1103 and the like.

  For example, in the case of the terminal structure (I), assuming that the integral value A of δ4.9 to 5.1 (2H) and the total integral value derived from the propylene-based polymer are B, the terminal structure (I) per 1000 carbon atoms Is obtained by the formula of 1000 × (A / 2) / (B / 2). When determining the ratio of other terminal structures, it should be replaced with the integrated value of the peak attributed to each structure while paying attention to the ratio of hydrogen.

  The proportion of terminal structure (I) in the terminal unsaturation is usually 30% or more, preferably 50% or more, more preferably 60% or more. The proportion of the terminal structure (I) in the terminal unsaturation described above is the sum of the numbers of the terminal structures (I) to (IV) existing per 1000 carbon atoms contained in the terminal unsaturated polypropylene. The ratio of the number of terminal structures (I) present per 1000 carbon atoms is expressed as a percentage.

The transition metal compound [A] functions as a polymerization catalyst for producing terminally unsaturated polypropylene in combination with the compound [C] described later.
As an olefin polymerization catalyst for producing terminally unsaturated polypropylene, Resconi, L .; Although known for a long time in JACS 1992, 114, 1025-1032, etc., the side chain of the olefin copolymer [R1] is isotactic or syndiotactic terminal unsaturated polypropylene, more preferably isotactic. Tic terminally unsaturated polypropylene is preferred.

  As the transition metal compound [A] contained in the olefin polymerization catalyst used for producing such a highly stereoregular polypropylene having a terminal structure (I) and a high content of terminal unsaturated polypropylene, a transition metal compound [A] can be used. The compounds disclosed in JP-A No. 1000579, JP-T-2001-525461, JP-A-2005-336091, JP-A-2009-299046, JP-A-11-130807, JP-A-2008-285443 and the like can be suitably used.

  More specifically, examples of the transition metal compound [A] include compounds selected from the group consisting of bridged bis (indenyl) zirconocenes or hafnocenes. More preferred is dimethylsilyl bridged bis (indenyl) zirconocene or hafnocene. More preferably, it is dimethylsilyl-bridged bis (indenyl) zirconocene, and by selecting zirconocene, generation of a long-chain branched polymer caused by insertion reaction of terminal unsaturated polypropylene is suppressed, and olefin resin (β) and olefin resin The propylene-based resin composition containing the resin (β) exhibits desired physical properties. On the other hand, when a large amount of the long-chain branched polymer is produced in the step (A), the propylene resin composition containing the olefin resin (β) and the olefin resin (β) has physical properties such as heat resistance and mechanical strength. There is a risk of damage.

  More specifically, dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride or dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl can be used as a suitable compound.

Step (A) can be carried out in any of gas phase polymerization, slurry polymerization, bulk polymerization, and solution (dissolution) polymerization, and the polymerization form is not particularly limited.
When the step (A) is performed by solution polymerization, examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination of two or more. Of these, hexane is preferred from the viewpoint of reducing the load of the post-treatment process.

  In addition, the polymerization temperature in step (A) is usually in the range of 50 to 200 ° C, preferably in the range of 80 to 150 ° C, more preferably in the range of 80 to 130 ° C, and by appropriately controlling the polymerization temperature, It becomes possible to obtain a terminally unsaturated polypropylene having a desired molecular weight and stereoregularity.

  The polymerization pressure in the step (A) is usually a normal pressure to 10 MPa gauge pressure, preferably a normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be performed in any of batch, semi-continuous and continuous methods. It can be carried out. In the present invention, among these, it is preferable to employ a method in which a monomer is continuously supplied to a reactor to carry out copolymerization.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours. It is.

  In the step (A), the polymer concentration is 5 to 50 wt%, preferably 10 to 40 wt% during steady operation. From the viewpoint of viscosity limitation in the polymerization ability, load of the post-treatment process (desolvation) and productivity, it is preferably 15 to 50 wt%.

  The weight average molecular weight of the terminal unsaturated polypropylene produced in the step (A) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 60,000, and further preferably. Is in the range of 10,000-60,000. By being a terminal unsaturated polypropylene having a weight average molecular weight within the above range, in the step (B) described later, the molar concentration of the terminal unsaturated polypropylene can be relatively increased with respect to ethylene or α-olefin. The efficiency of introduction into the chain is increased. On the other hand, when exceeding the said range, the molar concentration of terminal unsaturated polypropylene will become relatively low, and the introduction | transduction efficiency to a principal chain will become low. Moreover, when it is less than the above range, there may be practical problems such as a decrease in melting point.

  The molecular weight distribution (Mw / Mn) of the terminal unsaturated polypropylene produced in the step (A) is 1.5 to 3.0, typically about 1.7 to 2.5. In some cases, a mixture of terminally unsaturated polypropylenes having different molecular weights may be used.

The ratio of terminal unsaturation measured by ¹ H-NMR of the terminal unsaturated polypropylene produced in the step (A) is usually 0.1 to 6 per 1000 carbon atoms, more preferably 0.4 to 3.0. Furthermore, the proportion of terminal unsaturation having the terminal structure (I), so-called terminal vinyl amount, is usually 0.1 to 2.0 per 1000 carbon atoms, preferably 0.2 to 2.0. It is in the range. When the amount of terminal vinyl is small, the amount of the terminal unsaturated polypropylene introduced into the main chain in the subsequent step (B) becomes low, and the amount of the graft polymer [R1] produced decreases, so that the desired effect cannot be obtained. There is a case.

The amount of terminal unsaturation and the ratio of each terminal structure by ¹ H-NMR measurement can be performed according to the method described in, for example, Macromolecular Rapid Communications 2000, 1103, as described above.

[Process (B)]
Step (B) is the following step (B1) or (B2) performed in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table.

(B1) A step of copolymerizing the unsaturated terminal polypropylene produced in (A), ethylene, and at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms (B2) (A The process of copolymerizing the unsaturated terminal polypropylene produced in) and ethylene

  In the step (B), it is preferable that the α-olefin is used together with ethylene in the copolymerization. That is, the step B is preferably the step (B1) performed in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table. In other words, in the step B, in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table, the unsaturated terminal polypropylene produced in (A), ethylene, and 3 to 20 carbon atoms. It is preferably a step of copolymerizing at least one α-olefin selected from α-olefins.

  The group 4 transition metal compound of the periodic table is not particularly limited, but is preferably a group 4 transition metal compound including a ligand having a cyclopentadienyl skeleton. The transition metal compound of Group 4 of the periodic table is more preferably a bridged metallocene compound represented by the following general formula [B]. That is, it is preferable to perform the step (B) in the presence of an olefin polymerization catalyst containing a crosslinked metallocene compound represented by the following general formula [B].

  The bridged metallocene compound represented by the following general formula [B] is also referred to as a bridged metallocene compound [B].

（式［Ｂ］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹およびＲ¹²はそれぞれ独立に水素原子、炭化水素基、ケイ素含有基またはケイ素含有基以外のヘテロ原子含有基を示し、Ｒ¹〜Ｒ⁴のうち相互に隣り合う二つの基同士は互いに結合して環を形成していてもよい。

(In the formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. A hetero atom-containing group is shown, and two groups adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R ⁶ and R ⁷ may bond to each other to form a ring, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represents an aryl group.
Y ¹ represents a carbon atom or a silicon atom.
M ¹ represents a zirconium atom or a hafnium atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )

  In the step (B), it is important to select a catalyst that exhibits sufficient activity at a high temperature, has high copolymerizability and can have a high molecular weight. Since the terminal vinyl polypropylene (the terminal structure (I)) has a methyl branch at the 4-position and has a sterically bulky structure, it is difficult to polymerize compared to a linear vinyl monomer. Moreover, terminal vinyl polypropylene is difficult to be copolymerized under low temperature conditions where the polymer is precipitated. For this reason, the catalyst is preferably required to exhibit a sufficient activity at a polymerization temperature of 90 ° C. or higher and to make the main chain have a desired molecular weight.

From such a viewpoint, in order to obtain the olefin resin (β) containing a large amount of the graft polymer [R1], the bridged metallocene compound [B] is preferably used in the step (B).
The bridged metallocene compound [B] is selected from terminal unsaturated polypropylene produced in the step (A), ethylene, and preferably an α-olefin having 3 to 20 carbon atoms in combination with the compound [C] described later. It functions as an olefin polymerization catalyst for copolymerizing at least one α-olefin.

Hereinafter, the characteristics of the chemical structure of the bridged metallocene compound [B] used in the present invention will be described.
The bridged metallocene compound [B] is structurally provided with the following features [m1] and [m2].

  [M1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other is a fluorenyl group having a substituent (hereinafter referred to as “substituted fluorenyl group”). Say.)

[M2] The two ligands are bonded by an aryl group-containing covalently bonded bridge portion (hereinafter also referred to as “bridge portion”) composed of a carbon atom or a silicon atom having an aryl group.
Hereinafter, the cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the bridge | crosslinking part, and other characteristics which bridge | crosslinking metallocene compound [B] have are demonstrated sequentially.

(Cyclopentadienyl group which may have a substituent)
In the formula [B], R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. As a structure for taking in pyrene well, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or ^one or more of R ¹ , R ² , R ³ and R ⁴ are methyl groups A structure in which the remainder is a hydrogen atom is particularly preferable.

(Substituted fluorenyl group)
In the formula [B], R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. Or a silicon-containing group is preferable.

R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and the hydrogen atom, the hydrocarbon group and the silicon-containing group preferable.

R ⁷ and R ¹⁰ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and the hydrogen atom, the hydrocarbon group, and the silicon-containing group are preferable.

R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.
However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the viewpoint of polymerization activity, R ⁶ and R ¹¹ are preferably not hydrogen atoms, more preferably R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms, and R ⁶ and R ¹¹ are not preferred. Are preferably the same group selected from a hydrocarbon group and a silicon-containing group, and R ⁷ and R ¹⁰ are particularly preferably the same group selected from a hydrocarbon group and a silicon-containing group.

It is also preferable that R ⁶ and R ⁷ are bonded to each other to form an alicyclic ring or an aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic ring or an aromatic ring.
Illustrative and preferred groups for R ^{5 to} R ¹² include, for example, a hydrocarbon group (hereinafter sometimes referred to as “hydrocarbon group (f1)”) (preferably a hydrocarbon group having 1 to 20 carbon atoms). Alternatively, a silicon-containing group (hereinafter sometimes referred to as “silicon-containing group (f2)”) (preferably a silicon-containing group having 1 to 20 carbon atoms) may be mentioned.

  In addition, examples of the substituent in the substituted cyclopentadienyl group include heteroatom-containing groups (excluding silicon-containing groups) such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups.

  Specific examples of the hydrocarbon group (f1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, linear hydrocarbon group such as n-nonyl group, n-decanyl group, allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group Group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1- Branched hydrocarbon group such as methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamanty group A cyclic saturated hydrocarbon group such as a group; a cyclic unsaturated hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group, and a nuclear alkyl substituent thereof; a saturated hydrocarbon such as a benzyl group and a cumyl group And a group in which at least one hydrogen atom of the group is substituted with an aryl group.

  The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms, such as a group in which a silicon atom is directly covalently bonded to the ring carbon of the cyclopentadienyl group. Specifically, an alkylsilyl group (eg, trimethylsilyl group) and an arylsilyl group (eg, triphenylsilyl group) can be mentioned.

  Specific examples of hetero atom-containing groups (excluding silicon-containing groups) include methoxy, ethoxy, phenoxy, N-methylamino, trifluoromethyl, tribromomethyl, pentafluoroethyl, and penta A fluorophenyl group is mentioned.

  Among the hydrocarbon groups (f1), linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n- Suitable examples include butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl and the like.

Examples of the substituted fluorenyl group in the case where R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic ring or an aromatic ring include the compounds represented by the following general formulas [II] to [VI]. The group which originates is mentioned as a suitable example.

(Bridged part)
In the formula [B], R ¹³ and R ¹⁴ each independently represents an aryl group, and Y ¹ represents a carbon atom or a silicon atom. The important point in the method for producing an olefin polymer is that the bridging atom Y ¹ of the bridging portion has R ¹³ and R ¹⁴ which are aryl groups which may be the same or different from each other. From the viewpoint of ease of production, it is preferable that R ¹³ and R ¹⁴ are the same.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more of aromatic hydrogen (sp2-type hydrogen) contained in the aryl group is substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2), a halogen atom, and a halogenated hydrocarbon group.

  Specific examples of the aryl group include unsubstituted aryl groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group; a tolyl group, an isopropylphenyl group, and n-butylphenyl. Group, alkyl group-substituted aryl group such as t-butylphenyl group, dimethylphenyl group; cycloalkyl group-substituted aryl group such as cyclohexylphenyl group; halogenated aryl group such as chlorophenyl group, bromophenyl group, dichlorophenyl group, dibromophenyl group A halogenated alkyl group-substituted aryl group such as (trifluoromethyl) phenyl group and bis (trifluoromethyl) phenyl group; The position of the substituent is preferably a meta position and / or a para position. Among these, a substituted phenyl group in which the substituent is located at the meta position and / or the para position is more preferable.

(Other features of bridged metallocene compounds)
In the formula [B], Q can be coordinated by a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a lone electron pair. Represents a neutral ligand, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

  Examples of the hydrocarbon group for Q include a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,1- Diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3 -A trimethylbutyl group and a neopentyl group are mentioned. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclohexylmethyl group, and a 1-methyl-1-cyclohexyl group.

Examples of the halogenated hydrocarbon group for Q include groups in which at least one hydrogen atom of the hydrocarbon group for Q is substituted with a halogen atom.
In the formula [B], M ¹ represents a zirconium atom or a hafnium atom, which is preferable in that the hafnium atom copolymerizes terminal unsaturated polypropylene with high efficiency and can be controlled to have a high molecular weight. It is important to ensure high productivity by using a catalyst having a performance capable of copolymerizing terminally unsaturated polypropylene with high efficiency and controlling the molecular weight. This is because it is desirable to carry out the reaction under high temperature conditions in order to ensure high productivity, but the generated molecular weight tends to decrease under high temperature conditions.

(Example of preferred bridged metallocene compound [B])
Specific examples of the bridged metallocene compound [B] are shown below. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [II], and octamethyltetrahydrodicyclopentafluorenyl is represented by the formula [III]. And dibenzofluorenyl means a group derived from a compound having the structure represented by the formula [IV], and 1,1 ′, 3,6,8,8′-hexamethyl- 2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [V], and 1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7- Dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [VI].

Examples of the bridged metallocene compound [B] include:
Diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) ( Dibenzofluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafniu Dichloride, diphenylmethylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium Dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (dimethyl Phenyl) -3,6-ditert-butylfluorenyl) ha Niumujikurorido, diphenylmethylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butylfluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-Hexamethyl-2,7-dihydro Cyclopentafluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl ) Hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadi) Enyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6 -Di-tert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7 (Dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) hafnium dichloride Di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ', 8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfur Olenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclo Pentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl Hafnium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-chlorophenyl) methylene (cyclo Pentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfur Olenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclo Pentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl Hafnium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-chlorophenyl) methylene (cyclo Pentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,

Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadi) Enil) (1,1 ', 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6, 6 ', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) ) Methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) Hafnium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-bromophenyl) methylene (Cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichlorine Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (M-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) ( 2,3,6,7-tetra-tert-butylfluorenyl) hafnium dichloride,
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichlorine Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (P-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) ( 2,3,6,7-tetra-tert-butylfluorenyl) hafnium dichloride,
Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p- tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichloride, di (p tert-butyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-tert -Butyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-tert- Butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl) Ru-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopenta Dienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,3,3) 6,7-tetra-tert-butylfluorenyl) hafnium dichloride,

Di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p- n-butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Hafnium dichloride, di (pn-butyl-phenyl) methyle (Cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene ( Cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclo Pentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- ( Limethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6 -Ditert-butylfluorenyl) hafnium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) hafnium dichloride,
Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexa Til-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7 -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p -Biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) ) Methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,3 , 6,7-tetra-tert-butylfluorenyl) hafnium dichloride,
Di (1-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2, -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopenta Fluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl)- 3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclope Tadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetra tert-butylfluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyl) Tetrahydrodicyclopentafluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2, -Dihydrodicyclopentafluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydrodicyclopenta Fluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl)- 3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclope Tadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetra tert-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorene) Nyl) hafnium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride,
Di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Hafnium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (3 , 6-ditert-butylfluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) ( Dibenzofluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafniu Dichloride, diphenylsilylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) hafnium Dichloride, diphenylsilylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylsilylene (cyclopentadienyl) (2,7- (dimethyl) Phenyl) -3,6-ditert-butylfluorenyl) Niumujikurorido, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetra-tert- butylfluorenyl) include hafnium dichloride.

  As the bridged metallocene compound [B], a compound obtained by replacing “dichloride” in the above exemplified compounds with “difluoride”, “dibromide”, “diaiodide”, “dimethyl” or “methylethyl”, etc., “cyclopentadienyl” To “3-tert-butyl-5-methyl-cyclopentadienyl”, “3,5-dimethyl-cyclopentadienyl”, “3-tert-butyl-cyclopentadienyl” or “3-methyl-cyclo A compound replaced with “pentadienyl” and the like can also be mentioned.

  The above bridged metallocene compound can be produced by a known method, and the production method is not particularly limited. Examples of known methods include the methods described in WO 01/27124 and WO 04/029062 by the applicant.

The above bridged metallocene compound [B] is used singly or in combination of two or more.
The step (B) can be carried out in solution (dissolution) polymerization, and the polymerization conditions are not particularly limited as long as a solution polymerization process for producing an olefin polymer is used. However, the step (B) has a step of obtaining the following polymerization reaction solution. Is preferred.

The step of obtaining a polymerization reaction liquid is preferably a bridged metallocene compound [B], more preferably R ¹³ bonded to Y ¹ in the general formula [B], using an aliphatic hydrocarbon as a polymerization solvent. ^In the presence of a catalyst for olefin polymerization, wherein ¹⁴ is a phenyl group, or a phenyl group substituted by an alkyl group or a halogen group, and R ⁷ and R ¹⁰ each include a bridged metallocene compound [B] having an alkyl substituent. This is a step of obtaining a polymerization reaction solution of a copolymer of terminal unsaturated polypropylene produced in (A), ethylene, and preferably an α-olefin having 3 to 20 carbon atoms.

  In step (B), the terminal unsaturated polypropylene produced in step (A) is fed to the reactor in step (B) in the form of a solution or slurry. The feeding method is not particularly limited. Even if the polymerization solution obtained in step (A) is continuously fed to the reactor in step (B), the polymerization solution in step (A) is temporarily buffered. You may feed to a process (B), after storing in a tank.

  Examples of the polymerization solvent in the step (B) include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination of two or more. Further, the polymerization solvent in step (B) may be the same as or different from the polymerization solvent in step (A). Of these, aliphatic hydrocarbons such as hexane and heptane are preferable from the industrial viewpoint, and hexane is preferable from the viewpoint of separation and purification from the olefin resin (β).

  Moreover, it is preferable that the polymerization temperature of a process (B) is 90 degreeC or more, the range of 90-200 degreeC is more preferable, and it is especially preferable that it is the range of 100-200 degreeC. Such a temperature is preferable because the temperature at which the terminal unsaturated polypropylene is satisfactorily dissolved in aliphatic hydrocarbons such as hexane and heptane, which are preferably used industrially as the polymerization solvent, is 90 ° C. or higher. is there. A higher temperature is preferable for improving the amount of polypropylene side chain introduced. Furthermore, it is preferable that it is higher temperature also from a viewpoint of productivity improvement.

  The polymerization pressure in the step (B) is usually a normal pressure to 10 MPa gauge pressure, preferably a normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be performed in any of batch, semi-continuous and continuous methods. It can be carried out. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. In the present invention, among these, it is preferable to employ a method in which a monomer is continuously supplied to a reactor to carry out copolymerization.

  The reaction time in step (B) (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

  In the step (B), the polymer concentration is 5 to 50 wt%, preferably 10 to 40 wt% during steady operation. From the viewpoints of viscosity limitation in polymerization ability, post-treatment process (desolvation) load, and productivity, the content is preferably 15 to 35 wt%.

  The molecular weight of the resulting copolymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the usage-amount of compound [C] mentioned later. Specific examples of the compound [C] used for adjusting the molecular weight include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

[Compound [C]]
The method for producing the olefin resin (β) according to the present invention will be described later together with the transition metal compound [A] and the bridged metallocene compound [B] used as the olefin polymerization catalyst in the steps (A) and (B) described above. It is preferable to use compound [C].

  Compound [C] reacts with transition metal compound [A] and bridged metallocene compound [B] to function as a catalyst for olefin polymerization. Specifically, [C1] organometallic compound, [C2] It is selected from an organoaluminum oxy compound and a compound that forms an ion pair by reacting with a [C3] transition metal compound [A] or a bridged metallocene compound [B]. Hereinafter, the compounds [C1] to [C3] will be sequentially described.

([C1] organometallic compound)
Specific examples of the [C1] organometallic compound used in the present invention include an organoaluminum compound represented by the following general formula (C1-a), a Group 1 metal of the periodic table represented by the general formula (C1-b), and Examples thereof include complex alkylated products with aluminum, and dialkyl compounds of Group 2 or Group 12 metals represented by the general formula (C1-c). Note that the [C1] organometallic compound does not include the [C2] organoaluminum oxy compound described later.

上記一般式（Ｃ１−ａ）中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは０＜ｐ≦３、ｑは０≦ｑ＜３、ｒは０≦ｒ＜３、ｓは０≦ｓ＜３の数であり、かつｐ＋ｑ＋ｒ＋ｓ＝３である。）

In the general formula (C1-a), R ^a and R ^b may be the same as or different from each other, each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and p + q + r + s = 3. )

上記一般式（Ｃ１−ｂ）中、Ｍ³はＬｉ、ＮａまたはＫを示し、Ｒ^cは炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示す。）

In the above general formula (C1-b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. )

上記一般式（Ｃ１−ｃ）中、Ｒ^dおよびＲ^eは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｍ⁴はＭｇ、ＺｎまたはＣｄである。

In the general formula (C1-c), R ^d and R ^e may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ represents Mg. Zn or Cd.

  Examples of the organoaluminum compound represented by the general formula (C1-a) include compounds represented by the following general formulas (C-1a-1) to (C-1a-4).

（式中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、ｐは０＜ｐ≦３、好ましくは１．５≦ｐ≦３の数である。）で表される有機アルミニウム化合物。

(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is 0 <p ≦ 3, preferably 1.5 ≦ p ≦ 3)).

（式中、Ｒ^aは炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは０＜ｐ≦３、好ましくは０＜ｐ＜３の数である。）で表される有機アルミニウム化合物。

(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is 0 <p ≦ 3, preferably 0 <p <3. An organoaluminum compound represented by the formula:

（式中、Ｒ^aは炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、ｐは０＜ｐ≦３、好ましくは２≦ｐ＜３の数である。）で表される有機アルミニウム化合物。

(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is a number of 0 <p ≦ 3, preferably 2 ≦ p <3). Organoaluminum compound.

（式中、Ｒ^aおよびＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｙはハロゲン原子を示し、ｐは０＜ｐ≦３、ｑは０≦ｑ＜３、ｓは０≦ｓ＜３の数であり、かつｐ＋ｑ＋ｓ＝３である。）で表される有機アルミニウム化合物。

(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p represents 0. <P ≦ 3, q is a number of 0 ≦ q <3, s is a number of 0 ≦ s <3, and p + q + s = 3).

More specifically, as an organoaluminum compound belonging to the general formula (C1-a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkylaluminums such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
R ^a _2.5 Al (OR ^b ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 (wherein R ^a and R ^b may be the same or different from each other and have a carbon atom number of 1 to 15, preferably 1 to 4 hydrocarbon groups)
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

A compound similar to (C1-a) can also be used in the present invention, and examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the general formula (C1-b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
Examples of the compound belonging to the general formula (C1-c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n- Examples thereof include butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, and diethyl cadmium.

  In addition, [C1] organometallic compounds include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, Butyl magnesium bromide, butyl magnesium chloride and the like can also be used.

In addition, a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium is used as the [C1] organometallic compound. You can also
[C1] organometallic compounds as described above are used singly or in combination of two or more.

([C2] organoaluminum oxy compound)
The [C2] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687. Good. [C2] Specific examples of the organoaluminum oxy compound include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.
A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.

  (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.

  (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (C1-a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The above organoaluminum compounds are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, it is preferably insoluble or hardly soluble in benzene.

  Examples of the [C2] organoaluminum oxy compound used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula (III).

（一般式（ＩＩＩ）中、Ｒ¹⁷は炭素原子数が１〜１０の炭化水素基を示し、４つのＲ¹⁸は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１〜１０の炭化水素基を示す。）

(In the general formula (III), R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{18 s} may be the same as or different from each other. 1-10 hydrocarbon groups are shown.)

  The organoaluminum oxy compound containing boron represented by the general formula (III) includes an alkyl boronic acid represented by the following general formula (IV) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. It can be produced by reacting at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

（一般式（ＩＶ）中、Ｒ¹⁹は前記一般式（ＩＩＩ）におけるＲ¹⁷と同じ基を示す。）

(In general formula (IV), R ¹⁹ represents the same group as R ¹⁷ in general formula (III).)

  Specific examples of the alkyl boronic acid represented by the general formula (IV) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (C1-a).

As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
The [C2] organoaluminum oxy compounds as described above are used singly or in combination of two or more.

([C3] Compound that reacts with transition metal compound [A] or bridged metallocene compound [B] to form an ion pair)
As the compound [C3] (hereinafter referred to as “ionized ionic compound”) that forms an ion pair by reacting with the transition metal compound [A] or the bridged metallocene compound [B] used in the present invention, Japanese Patent Application Laid-Open No. Hei 1 (1994). -501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in 1). Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group, etc.) is used. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

  Examples of the ionic compound include compounds represented by the following general formula (V).

（一般式（Ｖ）中、Ｒ²⁰はＨ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンであり、Ｒ²¹〜Ｒ²⁴は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）。

(In the general formula (V), R ²⁰ is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R ^{21 to} R ^24. May be the same or different from each other and are organic groups, preferably aryl groups or substituted aryl groups.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation; N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation, etc. dialkylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ²⁰ is preferably a carbonium cation or an ammonium cation, particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). ) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (M, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethyl) Yl) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4, Examples thereof include 6-pentamethylanilinium tetra (phenyl) boron.

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Mention may also be made of cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (VI) or (VII).

（式（ＶＩ）中、Ｅｔはエチル基を示す。）

(In the formula (VI), Et represents an ethyl group.)

（式（ＶＩＩ）中、Ｅｔはエチル基を示す。）

(In the formula (VII), Et represents an ethyl group.)

Specifically as a borane compound which is an example of an ionized ionic compound (compound [C3]), for example, decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of carborane compounds that are examples of ionized ionic compounds include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3- Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 , 7-dicarbaound decaborane, undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) L) Ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6- Carbadecaborate, tri (n-butyl) ammonium 6-carboundecaborate, tri (n-butyl) ammonium 7-carbundecaborate, tri (n-butyl) ammonium 7,8-dicarboundeborate, tri ( n-butyl) ammonium 2,9-dicarbaundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8- Ethyl-7,9-dicarbaoundeca Rate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundedecaborate, Anions such as tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salt of;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundeborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III , Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8 -Dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca) Metal carborane anions such as idride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) And the like.

  The heteropoly compound that is an example of the ionized ionic compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. A compound. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, lintongost vanadic acid, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tangostanodic acid, phosphomolybdotungstic acid , Phosphomolybdniobic acid, and salts of these acids, but are not limited thereto. In addition, the salt includes, for example, a metal of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. And organic salts such as salts and triphenylethyl salts.

  An isopoly compound which is an example of an ionized ionic compound is a compound composed of a metal ion of one kind of atom selected from vanadium, niobium, molybdenum and tungsten, and is regarded as a molecular ionic species of a metal oxide. Can do. Specific examples include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids, but are not limited thereto. The salt includes, for example, a salt of the acid with, for example, a metal of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, and the like. And organic salts such as triphenylethyl salt.

  The above ionized ionic compounds (compounds that react with [C3] transition metal compound [A] and bridged metallocene compound [B] to form ion pairs) are used singly or in combination of two or more. .

  In addition to the transition metal compound [A] and the bridged metallocene compound [B], when a [C2] organoaluminum oxy compound such as methylaluminoxane as a co-catalyst component is used in combination, the olefin compound exhibits a very high polymerization activity.

[C3] ionized ionic compounds as described above are used singly or in combination of two or more.
The organometallic compound [C1] has a molar ratio (C1 / M) of the organometallic compound [C1] to the transition metal atom (M) in the transition metal compound [A] in the step (A). ) Is used in such an amount that the molar ratio (C1 / M) to the transition metal atom (M) in the bridged metallocene compound [B] is usually 0.01 to 100,000, preferably 0.05 to 50,000. .

  The organoaluminum oxy compound [C2] is a molar ratio (C2 / M) of the aluminum atom in the organoaluminum oxy compound [C2] and the transition metal atom (M) in the transition metal compound [A] in the step (A). ), But in the step (B), the molar ratio (C2 / M) with the transition metal atom (M) in the bridged metallocene compound [B] is usually 10 to 500,000, preferably 20 to 100,000. Used.

  The ionized ionic compound [C3] has a molar ratio (C3 / M) between the ionized ionic compound [C3] and the transition metal atom (M) in the transition metal compound [A] in the step (A). In (B), the molar ratio (C3 / M) with the transition metal atom (M) in the bridged metallocene compound [B] is usually 1 to 10, preferably 1 to 5.

[Process (C)]
In addition to the steps (A) and (B), the method for producing the olefin resin (β) may include a step (C) for recovering the polymer produced in the step (B), if necessary. This step is a step of separating the organic solvent used in steps (A) and (B), taking out the polymer and converting it into a product form, and producing an existing polyolefin resin such as solvent concentration, extrusion degassing, pelletizing, etc. If it is a process, there is no special restriction.

<Molded body>
The molded product obtained from the olefin resin (β) of the present invention will be described. Olefin-based resin (β) is highly compatible with properties such as impact resistance and toughness derived from ethylene polymers, and properties derived from propylene-based polymers such as heat resistance and rigidity. Molded, extruded, blown, blow molded, extruded blow molded, injection blow molded, press molded, vacuum molded, calendar molded, foam molded, etc., can be molded into various molded products, and automobile parts It can be applied to various known applications such as containers for food and medical use, packaging materials for food and electronic materials, films, sheets, and tapes.

  In particular, a molded body made of an olefin resin (β) is excellent in transparency in addition to the balance of physical properties described above, and is therefore suitable for containers and packaging materials for food use and medical use that require visibility of contents.

  Examples of containers for food use and medical use include food containers such as tableware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, frozen dessert cups, cups, beverage bottles, retort containers, bottles Containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottle chemical containers, detergent containers, cosmetic containers, perfume containers, toner containers, etc. .

  Examples of packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorbent packaging materials, retort food packaging materials, and freshness. Retaining film, pharmaceutical packaging material, cell culture bag, cell inspection film, bulb packaging material, seed packaging material, film for vegetable / mushroom cultivation, heat-resistant vacuum forming container, side dish container, side dish cover, commercial wrap film, home use Wrap film, baking carton, etc. are mentioned.

  The molded body obtained from the olefin resin (β) may be a molded body obtained from the olefin resin (β) and components other than the olefin resin (β). Examples of components other than the olefin resin (β) include other resins, rubber, inorganic fillers, additives, and the like. Additives include weather resistance stabilizer, heat stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, dye, plasticizer, anti-aging agent, hydrochloric acid absorbent, antioxidant And crystal nucleating agents.

<Propylene-based resin composition>
The propylene resin composition of the present invention contains a propylene resin (α) and the olefin resin (β).

  Since the olefin resin (β) described above is well compatible with the propylene resin (α) at an arbitrary blending ratio, the propylene resin (α) and the olefin resin in the propylene resin composition of the present invention. The content ratio with the resin (β) is not particularly limited, but as a content ratio that improves the impact resistance and toughness while maintaining good properties such as rigidity and hardness inherent to the propylene resin, the propylene resin ( α) is preferably 50 to 98 parts by mass, more preferably 60 to 95 parts by mass, and still more preferably 65 to 95 parts by mass. Moreover, 2-50 mass parts is preferable, as for olefin resin ((beta)), More preferably, it is 5-40 mass parts, More preferably, it is 5-35 mass parts. However, the sum total of each mass part of propylene-type resin ((alpha)) and olefin resin ((beta)) is 100 mass parts.

  When the content ratio of the propylene resin (α) and the olefin resin (β) is in the above range, the propylene resin composition of the present invention maintains good physical properties such as the original rigidity and hardness of the propylene resin. Further, impact resistance and toughness are improved, and it can be suitably used for production of various molded products.

Next, the propylene-based resin (α) will be described below.
The propylene-based resin (α) is different from the olefin-based resin (β) and is a propylene homopolymer or selected from propylene, ethylene, and an α-olefin having 4 to 20 carbon atoms. It is composed of a copolymer with at least one α-olefin. The copolymer may be a random copolymer or a block copolymer. Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2 -Ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1- Hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, - decene, 1-undecene, 1-dodecene, and the like can be given. Of these, α-olefins of 1-butene, 1-pentene, 1-hexene and 1-octene can be preferably used.

  Propylene-type resin ((alpha)) may be comprised from the single polymer among the said polymers, and may be comprised from the some polymer. The propylene resin (α) is polymerized with a Ziegler-Natta catalyst or the like.

  As the propylene resin (α), any commercially available propylene resin can be used without particular limitation. Examples of commercially available propylene resins include so-called homopolypropylene resins, random polypropylene resins, and block polypropylene resins.

  Hereinafter, the preferable aspect of propylene-type resin ((alpha)) is demonstrated. The melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the propylene-based resin (α) is usually 0.1 to 500 g / 10 minutes. The lower limit of MFR is preferably 0.2 g / 10 min, more preferably 0.3 g / 10 min, and the upper limit is preferably 300 g / 10 min, more preferably 100 g / 10 min, particularly preferably 50 g / 10 min. is there. When the MFR of the propylene resin (α) is smaller than 0.1 g / 10 min, the dispersibility of the propylene resin (α) and the olefin resin (β) in the propylene resin composition deteriorates, and the resin composition The mechanical strength of the steel may be reduced. When the MFR of the propylene-based resin (α) is larger than 500 g / 10 minutes, the strength of the propylene-based resin (α) itself is lowered, and the mechanical strength of the resin composition may be lowered.

  MFR serves as an index of the molecular weight of the propylene-based resin (α), but the propylene-based resin (α) preferably further has a weight average molecular weight in terms of polypropylene determined by gel permeation chromatography (GPC), preferably 80,000 to 900,000. More preferably, it is in the range of 100,000 to 700,000, particularly preferably in the range of 150,000 to 700,000.

  Furthermore, the propylene resin (α) preferably has a tensile modulus of 500 to 3000 MPa, more preferably 600 to 2500 MPa, and even more preferably 650 to 2200 MPa. The tensile elastic modulus is a value obtained by measuring a 2 mm-thick press sheet at 23 ° C. in accordance with JIS K7113-2. When the propylene polymer (α) has a tensile modulus in the above range, the propylene resin composition containing the propylene polymer (α) has high rigidity and high hardness.

  The propylene-based resin composition according to the present invention can be blended with other resins, rubbers, inorganic fillers, organic fillers, etc. within a range not impairing the object of the present invention, and is also resistant to weathering and heat. Additives such as crystal nucleating agents such as agents, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants, etc. be able to. In the propylene-based resin composition according to the present invention, the amount of the other resin, other rubber, inorganic filler, additive and the like is not particularly limited as long as the object of the present invention is not impaired. Absent.

  The method for preparing the propylene-based resin composition in the present invention is not particularly limited, such as a melting method and a solution method, but practically a melt-kneading method is preferable. As a melt-kneading method, a melt-kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components are mixed uniformly with a Henschel mixer, a ribbon blender, a V-type blender, etc., together with the additives described in the additional component section if necessary, and then uniaxial or multiaxial kneading. It can be prepared by kneading with an extruder, kneading roll, batch kneader, kneader, Banbury mixer or the like.

  The melt kneading temperature of each component (for example, cylinder temperature for an extruder) is usually 170 to 250 ° C, preferably 180 to 230 ° C. Furthermore, the kneading order and method of each component are not particularly limited.

<Molded body of propylene-based resin composition>
The molded product obtained from the propylene-based resin composition of the present invention will be described. Since the propylene resin composition contains the graft polymer [R1] in the olefin resin (β), it is presumed that the ethylene polymer is well dispersed in the propylene resin. Therefore, the propylene resin composition can improve the impact resistance while maintaining the rigidity derived from the propylene-based resin, and is excellent in the balance between rigidity and impact resistance. Therefore, the propylene-based resin composition can be produced by various known molding methods such as injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. It can be molded into a molded body, and can be applied to various known applications such as automobile parts, containers for food use and medical use, packaging materials for food use and electronic material use, films, sheets and tapes.

In particular, since the propylene-based resin composition of the present invention is excellent in transparency in addition to the above balance of physical properties, it is suitable for containers and packaging materials for food use and medical use that require visibility of contents.
Examples of containers for food use and medical use include tableware, retort containers, frozen storage containers, retort pouches, microwave oven heat resistant containers, frozen food containers, frozen dessert cups, cups, beverage bottles and other food containers, retort containers, bottles Containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottle chemical containers, detergent containers, cosmetic containers, perfume containers, toner containers, etc. .

  Examples of packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorbent packaging materials, retort food packaging materials, and freshness. Retaining film, pharmaceutical packaging material, cell culture bag, cell inspection film, bulb packaging material, seed packaging material, film for vegetable / mushroom cultivation, heat-resistant vacuum forming container, side dish container, side dish cover, commercial wrap film, home use Wrap film, baking carton, etc. are mentioned.

Films, sheets, and tapes include, for example, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical components, protective films for lenses, protective films for electrical components and electrical appliances, protective films for mobile phones, and PCs. Protective films such as protective films, masking films, condenser films, reflective films, laminates (including glass), radiation resistant films, gamma ray resistant films, porous films,
Other uses include, for example, housings for home appliances, hoses, tubes, wire covering materials, insulators for high-voltage wires, cosmetic / perfume spray tubes, medical tubes, infusion tubes, pipes, wire harnesses, motorcycles / railways Interior materials for vehicles, aircraft, ships, etc., instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, seat back garnish, console box, armrest, airbag case lid, shift knob, assist grip, side step Mat, reclining cover, trunk seat, seat belt buckle, inner / outer molding, roof molding, belt molding and other molding materials, door seals, body sealing and other automotive sealing materials, glass run channels, mudguards, Automotive interior and exterior materials such as a rocking plate, step mat, license plate housing, automotive hose member, air duct hose, air duct cover, air intake pipe, air dam skirt, timing belt cover seal, bonnet cushion, door cushion, damping tire, Special tires such as static tires, car race tires, radio control tires, packing, automotive dust covers, lamp seals, automotive boot materials, rack and pinion boots, timing belts, wire harnesses, grommets, emblems, air filter packings, furniture / Skin materials for footwear, clothing, bags, building materials, etc., sealing materials for construction, waterproof sheets, building material sheets, gaskets for building materials, window films for building materials, iron core protection members, gaskets, doors, door frames, window frames, peripheral edges Baseboard, open frame, flooring, ceiling material, wallpaper, health supplies (eg, non-slip mats / sheets, anti-tip films / mats / sheets), health appliances, shock absorbing pads, protectors / protectors (eg : Helmets, guards), sports equipment (eg sports grips, protectors), sports armor, rackets, mouth guards, balls, golf balls, transport equipment (eg transport shock absorbing grips, shock absorbing sheets), vibration control Pallet, shock absorbing damper, insulator, shock absorbing material for footwear, shock absorbing foam, shock absorbing material such as shock absorbing film, grip material, miscellaneous goods, toys, shoe sole, shoe sole, shoe midsole / inner sole, Sole, sandals, suction cups, toothbrushes, floor materials, gymnastic mats, power tool members, agricultural equipment members, heat dissipation materials, transparent substrates, soundproofing materials, food After filling the bottle with baby food / dairy products / pharmaceuticals / sterilized water, etc., it is subjected to high-temperature treatment such as boiling and high-pressure steam sterilization. Packing materials, industrial sealing materials, industrial sewing machine tables, license plate housings, cap liners such as plastic bottle cap liners, stationery, office supplies, OA printer legs, FAX legs, sewing machine legs, motor support mats, audio protection Precision equipment such as vibration materials, OA equipment support members, OA heat-resistant packing, animal cages, beakers, measuring cylinders, laboratory instruments, optical measurement cells, costume cases, clear cases, clear files, clear sheets, desk mats, For use as a fiber, for example, non-woven fabric, non-stretchable Cloth, fiber, waterproof cloth, breathable fabric and cloth, disposable diapers, sanitary products, sanitary products, filters, bag filters, dust collection filters, air cleaners, hollow fiber filters, water purification filters, gas separation membranes, etc. .

  Propylene-based resin compositions are suitable for containers and packaging materials for food use and medical use that require visibility of the contents because they are excellent in transparency in addition to having a good balance between rigidity and impact resistance.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
In the following examples, physical properties of the olefin resin (β) and the like were measured by the following methods.

(Olefin resin (β), (β ′), resin (B) and physical properties of terminal unsaturated polypropylene)
(1) Measurement of melting points (Tm ₁ and Tm ₂ ) and heat of fusion ΔH Melting points (Tm ₁ and Tm ₂ ) and heat of fusion ΔT of Tm ₁ were measured by DSC measurement under the following conditions.

Using a differential scanning calorimeter [SII RDC220], a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, the temperature was lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then heated to 200 ° C. at a temperature raising rate of 10 ° C./min. The endothermic peak observed during the second temperature increase was taken as the melting peak, and the temperature at which the melting peak appeared was determined as the melting point (Tm ₁ and Tm ₂ ). Further, the heat of fusion ΔH of Tm ₁ was obtained by calculating the area of the melting solution peak. When the melting peak was multimodal, the area of the entire melting peak was calculated.

(2) Density The density (kg / m ³ ) of the resin was measured according to JIS K7112 (density gradient tube method).

(3) Thermal xylene-insoluble amount The sample was formed into a sheet having a thickness of 0.4 mm by hot pressing (180 ° C., heating 5 minutes—cooling 1 minute) and finely cut. About 100 mg was weighed, wrapped in a 325 mesh screen, and immersed in 30 ml of p-xylene at 140 ° C. for 3 hours in a sealed container. Next, the screen was taken out and dried at 80 ° C. until a constant weight was obtained for 2 hours or more. The thermal xylene insoluble amount (wt%) is represented by the following formula.

Ｗ１：試験前のスクリーンおよびサンプルの質量、Ｗ２：スクリーン質量、Ｗ３：試験後のスクリーンおよびサンプルの質量。

W1: Screen and sample mass before test, W2: Screen mass, W3: Screen and sample mass after test.

(4) Intrinsic viscosity measurement The intrinsic viscosity measurement [η] was measured in decalin at 135 ° C.
Specifically, about 20 mg of resin was dissolved in 25 ml of decalin, and then the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin was added to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner as described above.
This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).

(5) ¹³ C-NMR measurement For the purpose of confirming compositional ratio analysis of ethylene and α-olefin of resin and stereoregularity (isotactic pentad fraction (mmmm: [%])) of terminal unsaturated polypropylene The ¹³ C-NMR measurement was carried out under the following conditions.

Apparatus: AVANCE III500 CryoProbe Prodigy type nuclear magnetic resonance apparatus manufactured by Bruker Biospin Co., Ltd., measurement nucleus: ¹³ C (125 MHz), measurement mode: single pulse proton broadband decoupling, pulse width: 45 ° (5.00 μsec), number of points: 64 k , Measurement range: 250 ppm (−55 to 195 ppm), repetition time: 5.5 seconds, number of integrations: 512 times, measurement solvent: orthodichlorobenzene / benzene-d ₆ (4/1 v / v), sample concentration: ca . 60 mg / 0.6 mL, measurement temperature: 120 ° C., window function: exponential (BF: 1.0 Hz), chemical shift standard: benzene-d ₆ (128.0 ppm).

(6) ¹ H-NMR measurement In order to analyze the terminal structure of the terminal unsaturated polypropylene, ¹ H-NMR measurement was performed under the following conditions.

Apparatus: ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL, measurement nucleus: ¹ H (400 MHz), measurement mode: single pulse, pulse width: 45 ° (5.25 μsec), number of points: 32 k, measurement range: 20 ppm (− 4 to 16 ppm), repetition time: 5.5 seconds, integration number: 64 times, measurement solvent: 1,1,2,2, -tetrachloroethane-d2, sample concentration: ca. 60 mg / 0.6 mL, measurement temperature: 120 ° C., window function: exponential (BF: 0.12 Hz), chemical shift standard: 1,1,2,2, -tetrachloroethane (5.91 ppm).

(7) GPC measurement For molecular weight analysis of the polymer, GPC analysis was performed under the following conditions.
Apparatus: Waters Alliance GPC 2000 type, column: TSKgel GMH6-HTx2 TSKgel GMH6-HTLx2 (both manufactured by Tosoh Corporation, inner diameter 7.5 mm × length 30 cm), column temperature: 140 ° C., mobile phase: orthodichlorobenzene (0 0.025% dibutylhydroxytoluene), detector: differential refractometer, flow rate: 1.0 mL / min, sample concentration: 0.15% (w / v), injection volume: 0.5 mL, sampling time interval: 1 second Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation).

  The average molecular weight in terms of polystyrene obtained by the above measurement, the following olefin resins β′-1, β′-2, β′-3 are converted to polyethylene, and terminal unsaturated polypropylenes M-1, M-2 are Converted to polypropylene.

(8) TMA softening temperature In order to evaluate the heat resistance of the resin, the softening temperature was measured by a thermomechanical analyzer (TMA). For the olefin resin produced by the method described in the examples or comparative examples, using a hydraulic hot press molding machine set to 200 ° C., after preheating for 10 minutes, pressurize for 2 minutes and immediately set to 20 ° C. A 2 mm thick press sheet was produced by cooling for 4 minutes with a hot press molding machine.
The obtained press sheet was cut into 5 mm square, and a pressure of ² kgf / cm ² was applied to a flat indenter of 1.0 mmφ at a heating rate of 5 ° C./min using a thermomechanical analyzer (TMA) according to JIS K7196. And the needle entry temperature (° C.) was determined from the TMA curve, and was defined as the TMA softening temperature.

(9) Haze test A haze test was conducted to evaluate the transparency of the resin.
About the olefin resin manufactured by the method described in the examples or comparative examples, using a hydraulic hot press molding machine set to 200 ° C., after preheating for 10 minutes, pressurize for 2 minutes and immediately set to 20 ° C. A 0.2 mm thick press sheet was prepared by cooling for 4 minutes with a hot press molding machine.
The obtained press sheet was measured for haze according to JIS K7136.

(10) Impact resistance test (Charpy impact test)
A Charpy impact test was conducted to evaluate the impact resistance of the resin. About the olefin resin manufactured by the method described in the examples or comparative examples, using a hydraulic hot press molding machine set to 200 ° C., after preheating for 10 minutes, pressurize for 2 minutes and immediately set to 20 ° C. A 4 mm thick press sheet was prepared by cooling for 4 minutes with a hot press molding machine.
The Charpy impact test ([kJ / m ² ]) was measured and evaluated according to JIS K7111, under the following conditions.

<Test conditions>
Temperature: 0 ° C, 23 ° C
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
The notch is machining. Hereinafter, examples and comparative examples of the olefin resin (β) will be described. In some cases, polymerization is carried out a plurality of times in order to secure the amount of resin necessary for analysis and physical property evaluation.

[Example 1]
Step (A): Production of Terminally Unsaturated Polypropylene (M-1) Dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride used as a catalyst was synthesized according to the method disclosed in Japanese Patent No. 3737134. .

  After putting 1.5 L of toluene into a 2 L glass reactor sufficiently purged with nitrogen, the temperature was raised to 85 ° C. While stirring the inside of the polymerization vessel at 600 rpm, propylene was continuously supplied at 240 liter / hr to saturate the liquid phase and the gas phase. Subsequently, in a state where propylene was continuously supplied, 5.0 mL (7.5 mmol) of a toluene solution (1.5 mol / L) of methylaluminoxane (also referred to as PMAO) was added, and then dimethylsilylbis (2-methyl-4-fini). 6.0 mL (0.012 mmol) of a toluene solution (0.0020 mol / L) of ruindenyl) zirconium dichloride was added, and polymerization was performed at 85 ° C. for 30 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol. The obtained polymerization reaction liquid was added to 5 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain 63.4 g of a propylene polymer (terminal unsaturated polypropylene (M-1)). The analysis results of the obtained polymer are shown in Table 1.

Step (B): Production of Olefin Resin (β-1) Compound (1) represented by the following formula used as a catalyst was synthesized by a known method.
Into a glass reactor with an internal volume of 1 L sufficiently purged with nitrogen, 5.0 g of terminal unsaturated polypropylene (M-1) and 500 ml of xylene were added, and the temperature was raised to 100 ° C. to end unsaturated polypropylene (M-1). Was dissolved. While stirring the inside of the polymerization vessel at 600 rpm, ethylene, 1-butene, and hydrogen were continuously supplied at 120 liter / hr, 2.4 liter / hr, and 5.0 liter / hr, respectively. And the gas phase was saturated. Subsequently, in a state where ethylene, 1-butene and hydrogen were continuously supplied, 1.0 mL (1.00 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu ₃ Al) was added to the compound ( 1) toluene solution (0.0020 mol / L) in 5.0 mL (0.01 mmol), then toluene in triphenylcarbenium tetrakis (pentafluorophenyl) borate (also referred to as Ph ₃ CB (C ₆ F ₅ ) ₄ ) 6.25 mL (0.025 mmol) of the solution (4.0 mmol / L) was added to initiate polymerization.

Under normal pressure, the polymerization temperature was maintained at 100 ° C., and 20 minutes after the start of polymerization, 5.0 mL (0.01 mmol) of a toluene solution (0.0020 mol / L) of the compound (1) was added, and then triphenylcarbenium. 6.25 mL (0.025 mmol) of a toluene solution (4.0 mmol / L) of tetrakis (pentafluorophenyl) borate (also referred to as Ph ₃ CB (C ₆ F ₅ ) ₄ ) was added, and another 20 minutes under normal pressure, 100% Polymerization was carried out at 0 ° C. Thereafter, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymerization reaction solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain 22.8 g of an olefin resin (β-1). The analysis results of the olefin resin (β-1) are shown in Table 2.

  Table 1 shows the results of analyzing the resin (β'-1) obtained by polymerization in the same manner as in Example 1 except that the terminal unsaturated polypropylene (M-1) is not added in Comparative Example 1 described later. 3 shows. This resin (β′-1) was assumed to be a copolymer constituting the main chain of the olefin resin (β-1).

[Example 2]
An olefin-based resin was produced in the same manner as in Example 1 except that the step (B) was carried out by changing the supply amount of 1-butene to 3.6 liters / hr. 23.5g of olefin resin ((beta) -2) was obtained. Table 2 shows the analysis results of the olefin resin (β-2).

[Example 3]
An olefin resin was produced in the same manner as in Example 2 except that the step (B) was carried out with the amount of terminal unsaturated polypropylene (M-1) charged to 2.0 g. 19.7g of olefin resin ((beta) -3) was obtained. Table 2 shows the analysis results of the olefin resin (β-3).

[Example 4]
An olefin resin was produced in the same manner as in Example 2 except that the step (B) was carried out with the amount of terminal unsaturated polypropylene (M-1) charged to 10.0 g. 30.3g of olefin resin ((beta) -4) was obtained. Table 2 shows the analysis results of the olefin resin (β-4).

  The result of having analyzed resin ((beta) '-2) obtained by superposition | polymerizing like Example 2 except not adding terminal unsaturated polypropylene (M-1) in the below-mentioned comparative example 2 by the method as stated above is shown. 3 shows. This resin (β′-2) was assumed to be a copolymer constituting the main chain of the olefin resin (β-2), the olefin resin (β-3), and the olefin resin (β-4).

[Example 5]
Step (A): Production of Terminally Unsaturated Polypropylene (M-2) In a 1 L stainless steel autoclave thoroughly purged with nitrogen, 500 mL of toluene and a toluene solution of methylaluminoxane (also referred to as PMAO) under nitrogen flow (1. 5 mol / L) 0.67 mL (1.0 mmol) was added. Thereafter, the autoclave was closed and the temperature was raised to 85 ° C. Next, the propylene partial pressure was increased to 0.3 MPa while stirring the interior of the polymerization vessel at 600 rpm, and then maintained at 85 ° C. Therein, 1.0 mL (0.001 mmol) of a toluene solution (0.0010 mol / L) of dimethylsilylbis (2-methyl-4-finylindenyl) zirconium dichloride was injected to initiate polymerization. The pressure was maintained while continuously supplying propylene gas, the polymerization was carried out at 85 ° C. for 20 minutes, and then the polymerization was stopped by injecting 5 mL of methanol. The obtained polymerization reaction liquid was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours to obtain 14.9 g of terminal unsaturated polypropylene (M-2). The analysis results of the obtained polymer are shown in Table 1.

Step (B): Production of Olefin Resin (β-5) After placing 25.0 g of terminal unsaturated polypropylene (M-2) and 500 ml of xylene into a 1 L glass reactor sufficiently purged with nitrogen, The temperature was raised to 100 ° C. to dissolve the terminal unsaturated polypropylene (M-1). While stirring the inside of the polymerization vessel at 600 rpm, ethylene, 1-butene, and hydrogen were continuously supplied at 120 liter / hr, 2.4 liter / hr, and 5.0 liter / hr, respectively. And the gas phase was saturated. Subsequently, in a state where ethylene, 1-butene and hydrogen were continuously supplied, 1.0 mL (1.00 mmol) of a decane solution (1.0 mol / L) of triisobutylaluminum (also referred to as iBu ₃ Al) was added to the compound ( 1) toluene solution (0.0020 mol / L) in 5.0 mL (0.01 mmol), then toluene in triphenylcarbenium tetrakis (pentafluorophenyl) borate (also referred to as Ph ₃ CB (C ₆ F ₅ ) ₄ ) 6.25 mL (0.025 mmol) of the solution (4.0 mmol / L) was added, and polymerization was performed at 100 ° C. for 20 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol. The obtained polymerization reaction solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitate was washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain 34.6 g of an olefin resin (β-5). Table 2 shows the analysis results of the olefin resin (β-5).

An olefin resin was produced by polymerization in the same manner as in Example 5 except that the terminal unsaturated polypropylene (M-2) was not added. The obtained olefin resin (β′-3) was 10.6 g. The analysis results of the obtained olefin resin (β′-3) are shown in Table 3. This resin (β′-3) was assumed to be a copolymer constituting the main chain of the olefin resin (β-5).
When the impact resistance of the olefin resin (β-5) was evaluated by the above method, it was 1.07 kJ / m ² (test temperature 0 ° C.) and 3.49 kJ / m ² (test temperature 23 ° C.). .

[Comparative Example 1]
An olefin resin was produced in the same manner as in Example 1 except that the step (B) was carried out by polymerization without adding the terminal unsaturated polypropylene (M-1). The obtained olefin resin (β′-1) was 17.3 g. Tables 2 and 3 show the analysis results of the obtained olefin resin (β′-1).

[Comparative Example 2]
An olefin resin was produced in the same manner as in Example 2 except that the step (B) was carried out by polymerizing without adding the terminal unsaturated polypropylene (M-1). The obtained olefin resin (β′-2) was 18.7 g. The analysis results of the resulting olefin resin (β′-2) are shown in Table 2 and Table 3.

[Comparative Example 3]
After putting 5.0 g of terminal unsaturated polypropylene (M-1), 18.5 g of olefin-based resin (β′-2), and 500 ml of xylene in a glass reactor with an internal volume of 1 L, the temperature was raised to 100 ° C. The terminal unsaturated polypropylene (M-1) and the olefin resin (β′-2) were dissolved. The obtained solution was added to methanol to precipitate a polymer. The precipitate was dried under reduced pressure at 80 ° C. for 10 hours to obtain 23.5 g of resin (B-1). Table 2 shows the analysis results of the obtained olefin resin (B-1).

[Comparative Example 4]
In a 1 L glass reactor, 25.0 g of terminal unsaturated polypropylene (M-2), 9.6 g of olefin resin (β′-3), and 500 ml of xylene were added, and the temperature was raised to 100 ° C. The terminal unsaturated polypropylene (M-2) and the olefin resin (β′-3) were dissolved. The obtained solution was added to methanol to precipitate a polymer. The precipitate was dried under reduced pressure at 80 ° C. for 10 hours to obtain 34.6 g of resin (B-2). Table 2 shows the analysis results of the resulting olefin resin (B-2).

When the impact resistance of the olefin resin (B-2) was evaluated by the above method, it was 0.84 kJ / m ² (test temperature 0 ° C.) and 1.19 kJ / m ² (test temperature 23 ° C.). .
FIG. 1 is a plot of the relationship between the TMA softening temperature and haze in Examples 1-4 and Comparative Examples 1-2.

上記、実施例と比較例の対比について以下詳細に説明する。

The above comparison between the example and the comparative example will be described in detail below.

(Contrast of Examples 1-4 and Comparative Examples 1-2)
First, when Comparative Example 1 (resin β′-1) and Comparative Example 2 (resin β′-2), which are plain ethylene polymer resins, are compared, Comparative Example 1 (resin β′-1) is Comparative Example. It can be seen that the TMA softening temperature is higher than that of 2 (resin β′-2) and the heat resistance is improved. This is probably because Comparative Example 1 (resin β′-1) has a smaller proportion of 1-butene (α-olefin) than Comparative Example 2 (resin β′-2). Comparative Example 1 has a higher haze value than Comparative Example 2, that is, the transparency is inferior. That is, heat resistance and transparency tend to conflict with each other, and the balance shown by the broken line in FIG.
On the other hand, it can be seen that the olefin polymers shown in Examples 1 to 4 have both high transparency and heat resistance.

(Contrast of Examples 1-2 and Comparative Example 3)
Examples 1 and 2 (resin β-1 and resin β-2) have the balance indicated by the solid line in FIG. Comparative Example 3 in which the resin β′-1 corresponding to the copolymer constituting the main chain of the resin β-1 was simply blended with the terminal unsaturated polypropylene M-1 used for the production of the resins β-1 and β-2 In (resin B-1), both heat resistance and transparency are greatly inferior to those of Examples 1 and 2, and it can be seen that the above effect is due to the inclusion of the graft polymer [R1].

(Contrast between Example 5 and Comparative Example 4)
Comparative Example 4 is a resin (resin B-2) obtained by blending terminal unsaturated polypropylene M-2 with resin β′-3, the haze thereof being 47.6%, and the impact strength being 0.84 kJ / m ² (test Temperature 0 ° C.) and 1.19 kJ / m ² (test temperature 23 ° C.). On the other hand, the resin (resin β-5) obtained in Example 5 is a resin containing the graft polymer [R1], its haze is 15.0%, and the impact strength is 1.07 kJ / m ^2. (Test temperature 0 ° C.) 3.49 kJ / m ² (Test temperature 23 ° C.). From this, it can be seen that the inclusion of the graft polymer [R1] significantly improves the transparency, and also improves the impact resistance at room temperature and low temperature.

Claims (13)

An olefin having a main chain composed of an ethylene polymer and a side chain composed of a propylene polymer and having a graft polymer [R1] satisfying the following requirement (i) and satisfying the following requirement (I) Resin (β).
(I) The ethylene polymer constituting the main chain has a repeating unit derived from ethylene, and is a repeating unit derived from at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms. In the range of 0 mol% or more and less than 10 mol% in the main chain.
(I) The density is in the range of 895 to 925 kg / m ³ . The olefin resin (β) according to claim 1, which satisfies the following requirement (II).
(II) The melting point (Tm ₁ ) measured by differential scanning calorimetry (DSC) is in the range of 120 to 165 ° C. The olefin resin (β) according to claim 1 or 2, which satisfies the following requirement (III).
(III) The insoluble amount of hot xylene is less than 3.0% by mass. The olefin resin (β) according to any one of claims 1 to 3, wherein the graft polymer [R1] satisfies the following requirement (ii).
(Ii) The propylene-based polymer constituting the side chain has a repeating unit derived from propylene in the range of 95 to 100 mol% in the side chain, and at least selected from ethylene and an α-olefin having 4 to 20 carbon atoms. It has a repeating unit derived from one α-olefin in the range of 0 to 5 mol% in the side chain. The olefin resin (β) according to any one of claims 1 to 4, wherein the graft polymer [R1] satisfies the following requirement (iii).
(Iii) The isotactic pentad fraction (mmmm) of the propylene-based polymer constituting the side chain is 93% or more. The olefin resin (β) according to any one of claims 1 to 5, which satisfies the following requirement (IV).
(IV) The ratio of the repeating unit derived from ethylene is in the range of 10 to 95 mol% with respect to all repeating units. The manufacturing method of the olefin resin ((beta)) as described in any one of Claims 1-6 including the process of following (A) and (B).
(A) Propylene is polymerized in the presence of an olefin polymerization catalyst containing a transition metal compound [A] belonging to Group 4 of the periodic table containing a ligand having a dimethylsilylbisindenyl skeleton to produce terminally unsaturated polypropylene. Step (B) Unsaturated terminal polypropylene produced in the following step (B1) or (B2) (B1) (A), which is carried out in the presence of an olefin polymerization catalyst containing a transition metal compound of Group 4 of the periodic table A step of copolymerizing ethylene with at least one α-olefin selected from α-olefins having 3 to 20 carbon atoms (B2) unsaturated terminal polypropylene produced in (A), and ethylene Copolymerization process The method for producing an olefin resin (β) according to claim 7, wherein the Group 4 transition metal compound of the periodic table is a crosslinked metallocene compound represented by the following general formula [B].

(In the formula [B], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are each independently a hydrogen atom, hydrocarbon group, silicon-containing group or silicon-containing group. A hetero atom-containing group is shown, and two groups adjacent to each other among R ^{1 to} R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and R ⁷ and R ¹⁰ are a hydrogen atom, a hydrocarbon group, are the same atoms or the same group selected from heteroatom-containing groups other than silicon-containing group and a silicon-containing group, R ⁶ and R ⁷ may bond to each other to form a ring, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring; provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represents an aryl group.
Y ¹ represents a carbon atom or a silicon atom.
M ¹ represents a zirconium atom or a hafnium atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different. )   The method for producing an olefin resin (β) according to claim 7 or 8, wherein the step (B) is a solution polymerization process having a polymerization temperature of 90 ° C or higher.   The propylene-type resin composition containing a propylene-type resin ((alpha)) and the olefin resin ((beta)) as described in any one of Claims 1-6.   Contains 50 to 98 parts by mass of the propylene resin (α) and 2 to 50 parts by mass of the olefin resin (β) (the total of the propylene resin (α) and the olefin resin (β) is 100 parts by mass) The propylene-based resin composition according to claim 10.   The molded object obtained from the olefin resin ((beta)) as described in any one of Claims 1-6. The molded object obtained from the propylene-type resin composition of Claim 10 or 11 .

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